Surface-modified metal oxides prepared by precipitation in the presence of a copolymer having N-vinylamide units, production processes and use thereof in cosmetic preparations

• US 7,666,506 B2
• Filed: 05/30/2006
• Issued: 02/23/2010
• Est. Priority Date: 06/03/2005
• Status: Expired due to Fees

• Current Assignee: BASF AG (BASF SE)
• Original Assignee: BASF SE
• Inventors: Andre, Valerie, Bouillo, Nathalie, Rieger, Jens, Kissel, Jutta
• Primary Examiner(s): LE, HOA T
• Application Number:
  US11/915,909
• Publication Number:
  US 20080193759A1
• Time in Patent Office: 1,365 Days
• Field of Search: 428/403, 428/407, 427/212, 427/215, 427/221, 424/59, 424/69, 424/617, 424/641, 424/642, 424/646, 424/691
• US Class Current: 428/407
• CPC Class Codes: A61K 8/27 Zinc; Compounds thereof
• CPC Class Codes: A61K 8/817 Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen; Compositions or derivatives of such polymers, e.g. vinylimidazol, vinylcaprolactame, allylamines (Polyquaternium 6)
• CPC Class Codes: A61K 8/8182 Copolymers of vinyl-pyrrolidones. Compositions of derivatives of such polymers
• CPC Class Codes: A61Q 17/04 Topical preparations for affording protection against sunlight or other radiation; Topical sun tanning preparations
• CPC Class Codes: B82Y 30/00 Nanotechnology for materials or surface science, e.g. nanocomposites
• CPC Class Codes: C01P 2004/61 Micrometer sized, i.e. from 1-100 micrometer
• CPC Class Codes: C01P 2004/62 Submicrometer sized, i.e. from 0.1-1 micrometer
• CPC Class Codes: C01P 2004/64 Nanometer sized, i.e. from 1-100 nanometer
• CPC Class Codes: C09C 1/043 Zinc oxide
• CPC Class Codes: C09C 3/10 Treatment with macromolecular organic compounds C09C3/006 takes precedence
• CPC Class Codes: Y10T 428/2982 Particulate matter [e.g., sphere, flake, etc.]
• CPC Class Codes: Y10T 428/2998 including synthetic resin or polymer

Abstract

The present invention relates to surface-modified nanoparticulate metal oxides where the metal is chosen from the group consisting of aluminum, cerium, iron, titanium, zinc and zirconium, wherein the surface modification comprises a coating with a copolymer P comprising, as monomers,

• A) 1 to 99 mol % of a N-vinylamide N-vinylpyrrolidone and
• B) 99 to 1 mol % of a monomer comprising, per molecule, a free-radically polymerizable α,β-ethylenically unsaturated double bond and an anionogenic and/or anionic group,
  with the proviso that the copolymer P must comprise no further monomers chosen from the group consisting of C₈-C₃₀-alkyl esters of monoethylenically unsaturated C₃-C₈-carboxylic acids, N-alkyl- or N,N-dialkyl-substituted amides of acrylic acid or of methacrylic acid with C₈-C₁₈-alkyl radicals, or vinyl esters of aliphatic C₈-C₃₀-carboxylic acids.

Claims

1. A process for the preparation of a surface-modified nanoparticulate metal oxide, where the metal is chosen from the group consisting of aluminum, cerium, iron, titanium, zinc and zirconium, by

a. precipitation of the metal oxide from an aqueous or alcoholic solution of one of its metal salts,

b. separating off the precipitated metal oxide from the aqueous or alcoholic reaction mixture and

c. subsequent drying of the metal oxide,

wherein the precipitation of the metal oxide in process step a. takes place in the presence of a copolymer P which comprises, as monomers,

A) 1 to 99 mol % of a N-vinylamide and

B) 99 to 1 mol % of a monomer comprising, per molecule, one free-radically polymerizable α

,β

-ethylenically unsaturated double bond and one anionogenic and/or anionic group,

with the proviso that the copolymer P must comprise no further monomers chosen from the group consisting of C₈-C₃₀-alkyl esters of monoethylenically unsaturated C₃-C₈-carboxylic acids, N-alkyl- or N,N-dialkyl-substituted amides of acrylic acid or of methacrylic acid with C₈-C₁₈-alkyl radicals, or vinyl esters of aliphatic C₈-C₃₀-carboxylic acids.

2. The process according to claim 1, wherein the precipitation takes place in the presence of a copolymer P comprising, as component A), 50 to 99 mol % of N-vinylpyrrolidone and, as component B), 1 to 50 mol % of acrylic acid.

3. The process according to claim 2, wherein the metal salts are metal halides, acetates, sulfates or nitrates.

4. The process according to claim 2, wherein the precipitation takes place at a temperature in the range from 20°

C. to 100°

C.

5. The process according to claim 2, wherein the precipitation takes place at a pH in the range from 3 to 12.

6. The process according to claim 2 for the preparation of surface-modified nanoparticulate zinc oxide.

7. A surface-modified nanoparticulate metal oxide, obtainable by a process according to claim 2.

8. The process according to claim 1, wherein the metal salts are metal halides, acetates, sulfates or nitrates.

9. The process according to claim 8, wherein the precipitation takes place at a temperature in the range from 20°

C. to 100°

C.

10. The process according to claim 3, wherein the precipitation takes place at a pH in the range from 3 to 12.

11. The process according to claim 8 for the preparation of surface-modified nanoparticulate zinc oxide.

12. The process according to claim 1, wherein the precipitation takes place at a temperature in the range from 20°

C. to 100°

C.

13. The process according to claim 1, wherein the precipitation takes place at a pH in the range from 3 to 12.

14. The process according to claim 1 for the preparation of surface-modified nanoparticulate zinc oxide.

15. The process according to claim 14, wherein the precipitation of the zinc oxide in process step a. takes place from an aqueous solution of zinc(II) chloride, zinc(II) nitrate or zinc(II) acetate at a temperature in the range from 25 to 40°

C. and a pH in the range from 7 to 11 in the presence of the copolymer P.

16. A surface-modified nanoparticulate metal oxide, obtainable by a process according to claim 1.

17. The surface-modified metal oxide according to claim 16, wherein the metal oxide particles have an average primary particle diameter of from 5 to 10000 nm.

18. The method for producing cosmetic preparations comprising the surface-modified nanoparticulate metal oxides as defined according to claim 16.

19. The method of producing according to claim 18 for producing cosmetic sunscreen preparations.

20. A cosmetic preparation comprising surface-modified nanoparticulate metal oxides defined according to claim 16.